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TALANTA · 2024 · IF 5.6

A semiconductor SERS sensor of corrosion-resistant PPy/GO composite film by electrochemical growth for detecting crystal violet residues in fresh fish tissue

Xishun Peng,Qixin chen,Xinghua Li,Li Yang,Yiheng Yuan,Cheng Zuo,Zhangyu Zhou,Zhongchen Bai

Crystal violet (CV) residues in Marine food have produced a severe health threat in human life. In this study, we proposed a semiconductor surface-enhanced Raman scattering (SERS) sensor of corrosion-resistant Polyaniline/Graphene oxide (PPy/GO) film by electrochemical growth method to detect CV residues in fresh fish tissue. A PPy/GO dispersion solution was one-step deposited on a stainless steel sheet surface by electrochemical polymerization process to form a PPy/GO composite film acting as a semiconductor SERS substrate. Since the substrate of PPy/GO film was mainly composed of GO sheet without other metals, it had a good corrosion resistance. The SERS enhancement factor and charge transfer intensity P CT of PPy/Go SERS substrate for CV molecules were up to 1.18 × 10 6 and 0.903, respectively. Furthermore, the limit of detection ( LOD ) of PPy/GO SERS substrate could reach 1.58 nM. In addition, SERS sensor of PPy/GO film could identify CV residues in fresh fish tissues, and its recovery rate was 91.8 %–107 %. This preparing method and detecting method we proposed PPy/GO SERS substrate provide a new pathway for detecting CV residues in Marine food.

研究领域: 材料科学 · 分析化学 · 环境科学 · 食品安全
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FOOD CHEMISTRY · 2024 · IF 8.5

Recyclable NiO/g-C3N4/ag hybrid substrates for sensitive SERS detection and photo-degradation of residual pesticides in beverages

Xiaojun Wen,Yiting Liu,Weilong Zhang,Lijun You,Ning Cai,Jumei Li

In this research, we fabricated an innovative NiO/CN/Ag composite through the straightforward electrostatic assembly of Ag nanoparticles and g-C 3 N 4 sheets onto NiO nanoflowers. This composite enables both surface enhanced Raman spectroscopy (SERS) detection and photo-degradation of pesticides. The results reveal NiO/CN/Ag can quantitatively detect thiram (TRM) and diquat dibromide (DQDB) in water, with a limit of detection (LOD) of 10 −9  M, and also exhibit outstanding photo-degradation efficiency, exceeding 95 % for TRM and DQDB within 90 min under simulated sunlight. Significantly, after the organic reagent (citric acid) on NiO/CN/Ag was completely removed through simulated solar irradiation, the signal-to-noise ratios of SERS spectra on NiO/CN/Ag were enhanced, achieving LODs of 10 −8  M for TRM and DQDB in different fruit juices and dried flower teas. Additionally, the composite demonstrate impressive recyclability, maintaining robust SERS signals and high degradation rates even after five cycles of “detection-degradation” processes.

CAS / MDL: 137-26-8 85-00-7
研究领域: 环境科学 · 分析化学 · 材料科学
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ACS Applied Materials & Interfaces · 2020 · IF 8.758

Optimizing the SERS Performance of 3D Substrates through Tunable 3D Plasmonic Coupling toward Label-Free Liver Cancer Cell Classification

Yu Han,Si-Rong Wu,Xiang-Dong Tian,Yun Zhang

Three-dimensional (3D) plasmonic nanostructures are emerging as excellent surface-enhanced Raman spectroscopy (SERS) substrates for chemical and biomedical applications. However, the correlation of 3D (including both in-plane and out-of-plane) plasmonic coupling with the SERS properties to deepen the understanding of 3D SERS substrates remains a challenge. Here, we perform correlation studies of 3D plasmonic coupling and SERS properties of the 3D hierarchical SERS substrates by tuning the multiscale structural elements. The effects of zero-dimensional (0D; the size of the building blocks), one-dimensional (1D; the thickness of the 3D substrates), and two-dimensional (2D; the composition of individual monolayers) structural elements on 3D plasmonic coupling are studied by performing UV–vis–near-infrared (NIR) spectroscopy and measuring SERS performance. It shows that both the extinction spectra and SERS enhancement are tuned at the 3D structural level. It is demonstrated that the plasmonic resonance wavelength (PRW) stemming from the 3D plasmonic coupling correlates with the SERS averaged surface enhancement factor (ASEF) and is improved by more than tenfold at the optimum 3D nanostructure. The optimized substrate is used to quantitatively analyze two small biological molecules. Moreover, as a proof-of-concept study, the substrate is first applied to differentiate between living liver normal and cancer cells with a high prediction accuracy through the spectral features of the cell membranes and the metabolites secreted outside the cells. We expect that the tuning of plasmonic coupling at the 3D level can open up new routes to design high-performance SERS substrates for wide applications.

研究领域: 生物医学工程 · 光谱学 · 癌症研究
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Hybridizing Silver Nanoparticles in Hydrogel for High-Performance Flexible SERS Chips

Mingming Chen,Jiaxin Zhang,Xiajun Zhu,Zhihong Liu,Jianli Huang,Xianchai Jiang,Fengfu Fu,Zhenyu Lin,Yongqiang Dong

An ideal surface-enhanced Raman scattering (SERS) substrate should have high sensitivity, long-term stability, excellent repeatability, and strong anti-interference. In the present work, single-layer carbon-based dot (CD)-capped Ag nanoparticle aggregates (a-AgNPs/CDs) with high SERS activity are synthesized and hybridized with a hydrogel to prepare novel hydrogel SERS chips. Benefiting from the unique properties of a-AgNPs/CDs and the hydrogel, the constructed hydrogel SERS chips show excellent performances. Taking crystal violet detection as an example, the hydrogel SERS chips show a detection limit of around 1 × 10–16 mol/L (high sensitivity), maintain above 96.40% of SERS activity even after 14 weeks of storage (long-term stability), and display point-to-point relative standard deviation (RSD) in one chip as low as 1.43% (outstanding repeatability) and RSD in different chips as low as 2.75% (excellent reproducibility). Furthermore, the self-extraction effect of the hydrogel enables the flexible hydrogel SERS chips to be used for analyzing various real samples including soybean milk, juices, and fruits without any complex pretreatment. For instance, the hydrogel SERS chips are able to detect trace thiram and 2-(4-thiazolyl)benzimidazole with the detection limits of 1 and 5 ppb in liquid samples, respectively, and of 1 and 2.5 ng/cm2 on the peel of fruits, respectively. The self-extraction functional flexible SERS chips offer a reliable and convenient platform for the quick detection and on-site monitoring of chemical contaminants.

研究领域: 材料科学 · 分析化学 · 纳米技术
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Ultrasensitive SERS quantitative detection of antioxidants via diazo derivatization reaction and deep learning for signal fluctuation mitigation

Wenhui Li,Yingxin Chen,Xin Li,Yi Zhong,Pei Xu,Yuanjie Teng

Synthetic antioxidants serve as essential protectors against oxidation and deterioration of edible oils, however, prudent evaluation is necessary regarding potential health risks associated with excessive intake. The direct adsorption of antioxidants onto conventional surface-enhanced Raman scattering (SERS) substrates is challenging due to the presence of phenolic hydroxyl groups in their molecular structures, resulting in weak Raman scattering signals and rendering direct SERS detection difficult. In this study, a diazo derivatization reaction was employed to enhance SERS signals by converting antioxidant molecules into azo derivatives, enabling the amplification of the weak Raman scattering signals through the strong vibrational modes induced by the N = N double bond. The resulting diazo derivatives were characterized using UV–visible absorption and infrared spectroscopy, confirming the occurrence of diazo derivatization of the antioxidants. The proposed method successfully achieved the rapid detection of three commonly used synthetic antioxidants, namely butylated hydroxyanisole (BHA), tert -butylhydroquinone (TBHQ), and propyl gallate (PG) on interfacial self-assembled gold nanoparticles. Furthermore, rapid predictions of BHA, PG, and TBHQ within the concentration range of 1 × 10 −6 to 2 × 10 −3 mol/L were achieved by integrating a convolutional neural network model. The predictive range of this model surpassed the traditional quantitative method of manually selecting characteristic peaks, with linear coefficients (R 2 ) of 0.9992, 0.9997, and 0.9997, respectively. The recovery of antioxidants in real soybean oil samples ranged from 73.0 % to 126.4 %. Based on diazo derivatization, the proposed SERS method eliminates the need for complex substrates and enables the analysis and determination of synthetic antioxidants in edible oils within 20 min, providing a convenient analytical approach for quality control in the food industry.

研究领域: 分析化学 · 食品科学 · 生物医学工程
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Nanoscale · 2014 ·Vol. 6 ·期 23 ·14514-14522 · IF 6.739

Mesoporous titania based yolk–shell nanoparticles as multifunctional theranostic platforms for SERS imaging and chemo-photothermal treatment

Weiwei Zhang,Yunqing Wang,Xiuyan Sun,Wenhai Wang,Lingxin Chen

Recently surface-enhanced Raman scattering (SERS) imaging guided theranostic nanoplatforms have attracted considerable attention. Herein, we developed novel yolk–shell gold nanorod@void@mesoporous titania nanoparticles (AuNR@void@mTiO2 NPs) for simultaneous SERS imaging and chemo-photothermal therapy. Our work showed three highlighted features: first, we proposed a facile and versatile “up to down” SERS labeling strategy for the drug delivery system, in which “empty carriers” were pre-synthesized, followed by co-loading of Raman reporters on AuNR and anti-cancer drug doxorubicin (DOX) in mTiO2 in sequence. The acquired SERS signal was strong enough for tracking NPs at both living cells and mice levels. Second, we selected mTiO2 as a novel drug loading material instead of the widely used mesoporous silica (mSiO2). The mTiO2 shared satisfactory drug loading and release behavior as mSiO2 but it was chemically inert. This property not only provided a facile way to form a yolk–shell structure but also rendered it with superior structural stability in a biological system. Third, the near infrared (NIR) light absorbing property of the AuNR SERS substrate was also explored for drug release regulation and photothermal treatment. Significantly greater MCF-7 cell killing was observed when treated together with DOX-loaded NPs and NIR laser irradiation, attributable to the synergistic chemo-thermal therapeutic effect. Our results indicated the established SERS labeled yolk–shell NP as a promising theranostic platform and suggested its potential in vivo applications.

研究领域: 生物医学工程 · 纳米医学 · 肿瘤学
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BIOSENSORS & BIOELECTRONICS · 2024 · IF 10.7

CRISPR/dCas9-based hotspot self-assembling SERS biosensor integrated with a smartphone for simultaneous, ultrasensitive and robust detection of multiple pathogens

Han Jiang,Xiaofan Zhu,Jingran Jiao,Chao Yan,Kaiyong Liu,Wei Chen,Panzhu Qin

Accurate detection of multiple pathogens in the early stages of infection is critical for guiding treatment and saving patients' lives, but current methods are still challenged by low sensitivity, poor robustness and long turnaround times. Here, we report a CRISPR/dCas9-based hotspot self-assembling surface-enhanced Raman scattering (SERS) biosensor (called dCasSERS) and its integration with a smartphone to address these challenges. In this design, bacterial DNA was pre-amplified by loop-mediated isothermal amplification (LAMP), and the repeat sequences of the amplicons were recognized by CRISPR/dCas9, providing abundant sites for the assembly of gold nanoparticles (AuNPs) and forming numerous hotspots for SERS analysis. Using AuNPs labeled with different Raman molecules as reporters, the presence of Staphylococcus aureus ( S. aureus ), Pseudomonas aeruginosa ( P. aeruginosa ) and Escherichia coli O157:H7 ( E. coli O157:H7) could be dexterously converted into distinguishable SERS signals. CRISPR/dCas9-based amplicon-specific recognition and SERS hotspot self-assembly improved the specificity and sensitivity, enabling the biosensor to simultaneously detect three target pathogens down to 1 CFU/mL without any cross-reactivity. By introducing a rapid extraction procedure and a smartphone-integrated handheld Raman spectrometer, rapid on-site analysis of multiple pathogens could be achieved in less than 50 min. The accuracy and robustness of the biosensor were demonstrated by 500 real urine specimens. This study displays a new paradigm for CRISPR/Cas-based self-assembly of SERS hotspots and provides insight into the future development of pathogen screening tools.

CAS / MDL: 69-78-3
研究领域: 分子生物学 · 医学诊断 · 纳米技术
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2024 · IF 4

Monolayer graphene oxide-Au loaded compound (GO-Au) as a flexible, stable and sensitive SERS active substrate for detection of stonehouse clam toxin (STX)

Lijun Yin,Peipei Xu,Junjie Ren,Jing Shi,Runbing Huang,Yunzhen Liu,Yudong Lu,Ruiyun You

Stonehouse clam toxin (STX) is a prevalent neuroparalytic toxin found among shellfish toxins . When consumed by humans, it disrupts neuronal conduction , potentially leading to quadriplegia , headache , shock, and even respiratory failure-induced death. This study introduces a highly sensitive and specific method for detecting shellfish toxins . The approach involves utilizing graphene gold-loaded compounds alongside stone house clam toxin aptamers and their complementary chains. The layered structure of graphene creates numerous hot spots among nanoparticles , while its arched spatial configuration offers an enhanced specific surface area , resulting in improved Surface-Enhanced Raman Scattering (SERS). By combining the signaling molecule Bodipy R6G-modified Apt with GO-Au loading compounds, distinctive Raman characteristic peaks emerge. Due to the strong affinity between Apt and STX, the Apt carrying the signaling molecule migrates away from the SERS aptamer probe's surface, thereby attenuating the original SERS signal intensity and facilitating ultra-sensitive shellfish toxin detection. The detection limit for the toxin was determined to be 5.47 nM, with a recovery rate ranging from 97.60 % to 108.32 %, affirming the applicability of this design for quantitative and specific shellfish toxin detection, signifying its considerable practical significance.

CAS / MDL: 237429-33-3
研究领域: 毒理学 · 分析化学 · 纳米技术
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BIOSENSORS & BIOELECTRONICS · 2025 · IF 10.5

Water-stable perovskite/metallic nanocomposites-based SERS aptasensor for detection of neuron-specific enolase

Jiayi Miao,Yifan Liu,Yi Xiao,Congzheng Yuan,Qian Xu,Panpan Chen,Yang Jin,Liying Zhang,Hongliang He,Shuhu Du

Perovskite/metallic heterojunction-based surface enhanced Raman scattering (SERS) substrates have been proven to be capable of providing Raman enhancement. However, the inherent water instability and poor dispersibility of perovskite/metallic nanocomposites-based SERS substrates pose significant challenges to their application in aqueous environments. Herein, polydopamine (PDA)-encapsulated cesium lead bromide (CsPbBr 3 ) adsorbing gold nanoparticles (AuNPs), termed as CsPbBr 3 @PDA@AuNPs, is prepared as SERS substrate, which exhibits excellent water stability and SERS activity. Dopamine as organic ligand not only passivates surface defects during the growth of perovskite nanocrystals, but also forms porous PDA protective layer, effectively preventing degradation of perovskite in aqueous medium. Meanwhile, PDA with abundant functional groups and conjugated π structure will adsorb AuNPs and promote electron flow between CsPbBr 3 and AuNPs, resulting in strong SERS activity. Based on the results, a SERS aptasensor has been fabricated by conjugation between CsPbBr 3 @PDA@AuNPs and double-stranded DNA (dsDNA), which is composed of neuron-specific enolase (NSE) aptamer and partial complementary signal-stranded DNA (ssDNA). The working strategy of as-fabricated SERS aptasensor is based on the conformational change (of ssDNA)-triggered Raman response for the detection of NSE. Upon the addition of NSE, the specific binding of NSE aptamers to NSE can convert rigid dsDNA into a flexible ssDNA, and the Cy5 signal molecule modified at the end of ssDNA will close to CsPbBr 3 @PDA@AuNPs SERS substrate, generating significant Raman signals with the lower limit of detection (1.02 pg/mL) of NSE. The SERS aptasensor has broad application prospect in the field of life/medicine science fields (e.g. early diagnosis and screening of disease).

研究领域: 生物医学 · 分析化学 · 纳米技术
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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2024 · IF 4.1

Innovative Synthesis of Adhesive-Assisted and Recyclable Fe3O4@PD-Ag Photomagnetic Nanocomposites as SERS probes for Ultrasensitive Thiram Detection on Fruit Peels

Keyan Liu,Wei Feng,Yanru Li,Donglai Han,Tianna Wu,Kaiyue Li,Shuo Yang

Surface-enhanced Raman spectroscopy (SERS) with enormous advantages has emerged as a powerful tool for both highly sensitive structural detection of analytes and various imaging applications. A notable advancement in the realm of multifunctional SERS substrates is the integration of magnetic nanoparticles endowed with magnetic manipulation capabilities and noble metal nanoparticles exhibiting plasmonic resonance properties. This synergistic combination offers substantial practical benefits for trace analysis across diverse fields. In this paper, a new paradigm of Fe 3 O 4 @PEI-DTC-Ag (Fe 3 O 4 @PD-Ag) photomagnetic nanocomposites based on magnetic Fe 3 O 4 nanoparticles (NPs), the noble metal silver quantum dots (Ag QDs) and the adhesive layer polyethyleneimine dithiocarbamate (PEI-DTC) for convenient recycling and ultrasensitive SERS detection was developed by engineering hydrothermal and seed-growth methods. The SERS performance of the Fe 3 O 4 @PD-Ag substrates with varying amounts of Ag was evaluated by detecting 4-aminothiophenol (4-ATP). Among the tested samples, Fe 3 O 4 @PD-Ag-4 with a silver solution volume of 200 ml exhibited the optimal performance, showcasing an enhancement factor ( EF ) of 4.418 × 10 5 . Moreover, the relative standard deviations (RSDs) were calculated to be less than 11.5 %, demonstrating the SERS substrates exhibit good uniformity and spectral reproducibility. Of note, the SERS substrate has demonstrated successful trace detection of thiram molecules, achieving a limit of detection (LOD) of up to 10 -9 M. The intensity of SERS signals shows a linear correlation with the logarithm of thiram concentration, ranging from 10 -4 to 10 -9 M, thus providing compelling evidence for quantitative detection. Importantly, the Fe 3 O 4 @PD-Ag-4 SERS substrate also showcases outstanding performance for detecting thiram in real food, underscoring its significant potential for application in food safety monitoring.

研究领域: 分析化学 · 食品安全 · 纳米技术 · 光谱学
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Small · 2025 · IF 12.1

Monitoring Spatiotemporal Dynamics of Extracellular pH in Breast Tumor Spheroid and Tissue by SERS Microsensors

Zedong Zhang,Chunyan An,Jianguo Dong,Xuyu Zhang,Tianyu Shen,Dekun Wang,Xue Mi,Shijing Yue,Xiaoyue Tan,Yuying Zhang

Extracellular pH (pHe) acidification is a hallmark of solid tumors, linked to cancer initiation, progression, and drug resistance. Non-invasive monitoring of pHe spatiotemporal dynamics during cancer growth and in response to drug is crucial for understanding cancer mechanisms and developing novel therapeutic strategies. Here, a micro-sized pH sensor is developed by encapsulating Au@Ag@MBA nanosensors within biocompatible agarose hydrogel microspheres. These Aga microsensors in a size range of 3–10 µm, may avoid cellular endocytosis and stably reside in the extracellular environment. pHe dynamics are monitored via surface-enhanced Raman scattering (SERS) mapping in tumor spheroids and solid tumor tissues over 7 and 25-day periods, respectively. Distinct pH gradients are observed between the outer and core regions of the tumor spheroid, which evolved over time and are disrupted by doxorubicin treatment. In vivo, a decrease of average tumor pHe from ≈6.2 to ≈5.5 is observed with tumor progression, and doxorubicin administration resulted in a pHe elevation of ≈0.6 units. This microsensor-based SERS sensing approach provides a facile method for long-term monitoring of spatiotemporal dynamics within the disease microenvironment.

CAS / MDL: 9012-36-6 34819-78-8
研究领域: 肿瘤学 · 生物医学工程 · 分子影像学 · 纳米医学 · 肿瘤微环境
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2010 · IF 2.6

Preparation of 2-mercaptobenzothiazole-labeled immuno-Au aggregates for SERS-based immunoassay

Chunyuan Song,Zhuyuan Wang,Jing Yang,Ruohu Zhang,Yiping Cui

A detailed method for preparation of 2-mercaptobenzothiazole (MBT)-labeled immuno-Au aggregates as a novel Raman probe for SERS-based immunoassay has been proposed in this paper. The formation kinetics of gold aggregates induced by MBT and the impact of the amount of labeled reporter on the aggregation, as well as the fabrication of MBT-labeled immuno-Au aggregates were characterized comprehensively by UV–vis spectrophotometer . Meanwhile, a chain-like morphology of aggregates was monitored by TEM images. Experimental results show that this Raman tag can act as an efficient label and an enhanced Raman signal of SERS-based immunoassay can be obtained successfully with this novel probe. This work shows the method for the preparation of immune probe for SERS-based immunoassay using MBT as reporter and provides a reference for the preparation of immune probe with other Raman markers for multi-channel SERS-based immunoassay.

研究领域: 分析化学 · 纳米技术 · 生物传感器 · 免疫分析
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